Polyols containing carboxyl groups and production thereof

ABSTRACT

The present invention is directed to a low viscosity carboxyl-containing polyol composition having a viscosity in the range of about 3,000-100,000 centipoise, and having an oligomer content of less than 30 mg KOH/g. Preferably, the carboxyl-containing polyol has one ester group per molecule. The carboxyl-containing polyol is suitable for use in preparing low viscosity polyurethane prepolymers. Also disclosed is a method of producing this carboxyl-containing polyol composition by reacting a low molecular weight triol with an acid anhydride in the presence of 25-500 ppm of an inorganic or organic acid catalyst. The organic or inorganic acid is preferably selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, formic acid, proprionic acid, p-toluenesulfonic acid, oxalic acid, and combinations thereof. The present invention is also directed to methods of making the above carboxyl-containing polyols, as well as prepolymers and urethane polymers containing the above carboxyl-containing polyols.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a Continuation-in-Part application of U.S.patent application Ser. No. 09/723,263 filed Nov. 27, 2000.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates generally to low viscosity polyolssuitable for use in the synthesis of polyurethanes, and, moreparticularly, to carboxyl-containing polyols. These carboxyl-containingpolyols are made by reacting a low molecular weight polyol with adicarboxylic acid anhydride in the presence of 5-500 ppm of a catalystselected from the group consisting of organic acids, inorganic acids,and combinations thereof.

[0004] 2. Description of the Related Art

[0005] It is well known that polyurethanes are generally manufactured byreacting a polyisocyanate and a polyol. The resulting polyurethane mayhave unique chemical and/or mechanical properties depending on thereacting conditions, as well as other additives such as catalysts,solvents, surfactants, blowing agents, fillers, and the like. Thepolyols used in manufacturing polyurethanes are typically low molecularweight poly-hydroxyl-containing polymers, such as those containingpolyethers, polyesters, polyacrylics, polycarbonates, and the like.These polyols are generally provided with at least two hydroxyl groupsso that they can be easily incorporated into a lengthening polymer in anordered fashion.

[0006] Due to environmental and toxicity concerns, water-basedpolyurethanes and aqueous dispersions of polyurethanes are becoming thepreferred materials for many applications, including coatingapplications. However, in many instances, the components of thepolyurethane including coating applications. However, in many instances,the components of the polyurethane product are not easily soluble inwater. To overcome this problem, it is known to introduce ionizablegroups into the monomers prior to their condensation into the finalpolyurethane polymer. These ionizable groups aid in the solubilizationof the polymer and thus produce a uniform aqueous dispersion of thefinal polyurethane mixture.

[0007] The reaction of dicarboxylic acid anhydride with triols ortetrols has been described generally in U.S. Pat. No. 5,863,980 toKuen-Bae Choi. According to the disclosure, acid groups are attached tothe main chain via an ester bond in the absence of catalysts, includingacid catalysts. In order to perform the reaction between acid anhydrideand polyol, a high reaction temperature was used and resulted in highlyviscous polyols. When such highly viscous polyol is reacted with adiisocyanate, a viscous prepolymer is obtained, and this result is notdesired since the viscous prepolymer is difficult to process.

[0008] U.S. Pat. No. 4,207,2267 to Wulf von Bovin discloses a processfor preparation of stable suspensions of inorganic fillers inpoly-hydroxyl compounds by grafting olefinically unsaturated carboxylicacid onto polyol. As an example, acrylic acid and peroxide typeinitiators are used for this process.

[0009] U.S. Pat. No. 4,250,077 to Wulf von Bovin et al. discloses asuspension which is stable and contains inorganic filler and graftpolymer which was produced by free radical polymerization ofolefinically unsaturated carboxylic acid.

[0010] U.S. Pat. No. 4,460,738 to Frentzel et al. discloses a processfor grafting carboxyl groups to mono and polyether polyols by reactingmaleic acid, fumaric acid, itaconic acid or their mixtures withpolyether polyols in presence of peroxy-type free radical initiator.

[0011] U.S. Pat. No. 4,521,615 to Frentzel discloses carboxy-containingpolyols made by a free radical type addition reaction of fumaric ormaleic acid with a monoether or a polyether diol or triol. It is statedat column 6, lines 37-44 of the Frentzel patent that some or all of thecarboxylic acid groups on the carboxy-containing polyols can beneutralized with an organic or inorganic base. This patent alsodiscloses that the polyols are suitably further reacted to formprepolymers, and the carboxyl groups on the prepolymer are suitablyneutralized, e.g. with triethylamine (TEA), for forming dispersions (seecolumn 7, lines 42-60).

[0012] U.S. Pat. No. 6,103,822 to Housel et al. discloses a process forincorporating carboxyl groups into main polyester chain by reactingpolyether or polyester polyol with an aliphatic dianhydride.

[0013] U.S. Pat. Nos. 5,242,954 and 5,250,582 to Hire et al. disclose aprocess for making cellular and microcellular polyurethane foams using acarboxylic acid-grafted polyol.

[0014] U.S. Pat. No. 5,880,250, discloses the reaction of polyols withdianhydride “to form an acid functionalized polyol in which there arereactive hydroxyl groups, and neutralizable or reactive carboxylic acidgroups.” See Formula II at column 7 of the '250 patent. There are threeways by which carboxyl groups can be introduced into the polyolcomponent:

[0015] 1. Free Radical addition of unsaturated dicarboxylic acids topolyol through C—C double bond (U.S. Pat. Nos. 4,207,2267; 4,250,077;4,460,738; 4,521,6155; 242,954 and 5,250,582)

[0016] 2. Reacting a polyol with a dianhydride and producing polyestertype bonding (U.S. Pat. Nos. 6103822; 5,880,250)

[0017] 3. Reacting a triol or tetrol with an anhydride of dicarboxylicacid which binds the carboxyl group to polyol through an ester bond(U.S. Pat. No. 5,863,980)

[0018] A common result of introduction of a carboxyl group into thepolyol component, in accordance with the U.S. Pat. No. 5,863,980 is thatundesirable side reactions occur between the carboxyl group and nearbyhydroxyl groups. The side reactions, typically causing oligomers toform, markedly increase the viscosity of the monomer mixture, resultingin a decreased amount of usable monomers suitable for use in the finalaqueous urethane dispersion. In addition, the “side” reacted carboxylgroup results in reduced hydrophilicity of the final urethanedispersion.

[0019] Accordingly, there is a need for low viscosity polyols containingcarboxyl groups, and methodology for their production. Further, there isa need for low viscosity polyols that are suitably water soluble, andare useful in the preparation of low viscosity urethane dispersions. Thepresent invention provides an answer to those needs.

SUMMARY OF THE INVENTION

[0020] In one aspect, the present invention is directed to a lowviscosity carboxyl-containing polyol compostion having a viscosity inthe range of 3,000-100,000 centipoise, and having an oligomer content ofless than 30 g KOH/gm. This composition is obtained by reacting a polyolcontaining between two and four hydroxyl groups with an anhydride of adicarboxylic acid. Preferably, the polyol reactant is a triol, and thecarboxyl-containing polyol has one ester group and one carboxyl groupper molecule. The carboxyl-containing polyol is suitable for use inpreparing low viscosity polyurethane prepolymers.

[0021] In another aspect, the present invention is directed to a methodof producing this carboxyl-containing polyol composition by reacting alow molecular weight polyol containing between two and four hydroxylgroups and preferably a triol with a dicarboxylic acid anhydride in thepresence of 5-500 ppm of an inorganic or organic acid catalyst, formingan ester bond containing the carboxyl group. The organic or inorganicacid is preferably selected from the group consisting of hydrochloricacid, sulfuric acid, nitric acid, formic acid, proprionic acid,p-toluenesulfonic acid, oxalic acid, and combinations thereof.

[0022] In yet another aspect, the present invention is directed to amethod of preparing a carboxyl-containing monomer for use in preparationof a polyurethane polymer, comprising the step of combining a lowmolecular weight polyol compound and an dicarboxylic acid anhydride inthe presence of 5-500 ppm of an organic or inorganic acid(advantageously selected from the group consisting of hydrochloric acid,sulfuric acid, nitric acid, formic acid, proprionic acid,p-toluenesulfonic acid, oxalic acid, and combinations thereof, in orderto produce the carboxyl-containing monomer, the carboxyl-containingmonomer having a viscosity in the range of about 3,000 to about 100,000cps and having an oligomer content of less than about 30 mg KOH/g.

[0023] In still another aspect, the present invention relates to aprepolymer that is formed by reacting the carboxyl-containing polyol, ora partially or fully neutralized amine salt thereof, with apolyisocyanate.

[0024] In another aspect, the present invention is directed to awater-borne polyurethane polymer, the water-borne polyurethane polymerbeing the reaction product of (1) the prepolymer described above, and(2) an amine compound.

[0025] These and other aspects will become apparent upon reading thefollowing detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0026] It has been surprisingly found, in accordance with the presentinvention, that a low viscosity carboxyl-containing polyol compositionhaving a viscosity in the range of about 3,000-100,000 centipoise, andhaving an oligomer content of less than 30 mg KOH/g, is suitablyprepared in a straightforward fashion. Preferably, thecarboxyl-containing polyol has one ester group per molecule. Thecarboxyl-containing polyol is suitable for use in preparing lowviscosity polyurethane prepolymers.

[0027] Further, the present inventors have surprisingly discovered thatthe reaction of a low molecular weight polyol with an dicarboxylic acidanhydride, suitably effected in the presence of an organic or inorganicacid catalyst, suitably provides a low viscosity carboxyl-containingpolyol that can be advantageously employed in the production of lowviscosity polyurethane prepolymers for waterborne polyurethanedispersions. Also, the present inventors have unexpectedly discoveredthat organic and inorganic acid catalysts are very efficient incatalyzing polyol-anhydride addition reactions with anhydride ringopening mechanism, while exhibiting little or no acceleration of acidand polyol condensation side reactions.

[0028] The present invention provides a process for introducing carboxylgroups to polyol monomers, and the low-viscosity carboxyl-containingpolyol monomers made by the process. The carboxyl-containing polyols areprepared by reacting a polyol monomer, preferably containing threehydroxyl groups per molecule, with a dicarboxylic acid anhydride underconditions such that an organic acid group is introduced into the polyolmonomer. Because the polyol monomer is preferably selected to have threehydroxyl groups per molecule and is reacted with only one molecule ofanhydride, the resulting carboxyl-containing monomer possesses two freehydroxyl groups per molecule and one carboxyl group attached to thepolyol. As indicated above, the two free hydroxyl groups of thecarboxyl-containing monomer are used in subsequent reactions that formthe ultimate polyurethane, while the carboxyl group aids in hydration ofthe polyurethane dispersion and prevents generation of highly viscous,unwanted side reactions and undesirable by-products.

[0029] As defined herein, the term “polyol” refers to compounds havingbetween two and four free hydroxyl (—OH) groups per molecule, andpreferably three hydroxyl groups. As defined herein, the phrase “lowmolecular weight polyol” refers to those polyols having a molecularweight less than 8,000, more preferably less than 2,000, and mostpreferably less than 500. The phrase “carboxyl-containing monomer”refers to a polyol having a carboxyl group added to one of the hydroxylgroups of the polyol. The term “oligomer” refers to a product where morethan one polyol molecule is reacted with an acid anhydride.

[0030] As indicated above, in one aspect, the present invention isdirected to a carboxyl-containing polyol that is suitable for use inpreparing a polyurethane polymer. The carboxyl-containing polyol is thereaction product of a low molecular weight polyol compound and adicarboxylic acid anhydride, and the resulting carboxyl-containingmonomer has a viscosity in the range of 3,000-100,000 centipoise (cps)and has oligomer content in the range of 2-30 mg KOH/g. Each of thesecomponents are discussed in more detail below.

[0031] Examples of polyols that are useful in the present inventioninclude low molecular weight polyols having from two to four hydroxylgroups. Preferably, the polyol contains three free hydroxyl groups(hereinafter termed “triol”). Triols suitable for use in the presentinvention are generally based on the structure of glycerol,trimethylolpropane, trimethylolethane, triethanolamine,triisopropanolamine and the like. Preferred triols include Poly-G 76-635(a polyether triol of nominal molecular weight 265, available from ArchChemicals, Inc.) and Poly-G 35-610 (a polyether triol of nominalmolecular weight 275), and their mixtures with trimethylolpropane orpure trimethylolpropane. Alternatively, polyalkylene polyether polyolsproduced by the poly-addition of any of the mentioned above triols andan alkylene oxide such as ethylene oxide, propylene oxide, butyleneoxide, epoxybutene, and the like, may also be used. These triolsgenerally have molecular weight from less than 100 to about 6000.

[0032] Suitable acid anhydrides used in the present invention includeany dicarboxylic acid anhydride that results in the addition of acarboxyl group to the polyol molecule. Useful acid anhydrides includemaleic anhydride, phthalic anhydride, succinic anhydride, glutaricanhydride, and mixtures thereof. A preferred acid anhydride is succinicanhydride.

[0033] The preparation of the carboxyl-containing polyol is generallyaccomplished by reacting the low molecular weight triol compound with adicarboxylic acid anhydride in the presence of an inorganic or anorganic acid catalyst. Advantageously, the resulting product has oneester bond per molecule. When employing an inorganic acid catalyst, thepolyol is suitably heated with anhydride to about 80-105° C. in presenceof the inorganic acid (preferably about 25-500 ppm of hydrochloric acid,sulfuric acid, or nitric acid, more preferably from about 50-250 ppmhydrochloric acid, sulfuric acid, or nitric acid, and most preferablyfrom about 100-200 ppm hydrochloric acid, sulfuric acid, or nitricacid). Suitable organic acids include formic acid, propionic acid,p-toluenesulfonic acid, oxalic acid, and combinations thereof, and theseorganic acids are suitably employed within the preferred ranges ofamounts as described above for the inorganic acids.

[0034] Without wishing to be bound by any particular theory, it isbelieved that the organic acid catalysts act as a proton source, whichadds to the anhydride of dicarboxylic acid and creates a cation. Thecation then quickly reacts by adding to the electronegative oxygen ofthe polyol. According to the present invention, addition of 5-500 ppm ofthe organic or inorganic acid catalyzes the selective reaction betweenpolyol and dicarboxylic acid anhydride, and an acid group is introducedinto the polyol molecule. Preferably, a triol is selected that has threehydroxyl groups per molecule. Each triol molecule is reacted with onemolecule of anhydride to generate a product that has two hydroxyl groupsper molecule and one ester group in the form of a carboxyl groupattached to the polyol. It is preferred that the molecule produced insuch addition reaction contains two hydroxyl groups, one carboxyl groupand one ester group. Such chemical structure is ideal to produce lowviscosity carboxyl polyols. To illustrate the relationship betweenchemical structure and carboxyl polyol viscosity we have plotted twographs (refer to FIG. 1 and FIG. 2). FIG. 1 illustrates the relationshipbetween carboxyl polyol viscosity and the number of ester groups in themolecule of carboxyl polyol. Carboxyl polyols in FIG. 1 were made byreacting 1 mole of glycerolpropoxylate ( Arch Chemicals product Poly-G76-635) with 1 mole of succinic anhydride. The Carboxyl polyols in FIG.2 were obtained by reacting 1 mole of trimethylolpropane with 1 mole ofsuccinic anhydride.

[0035] Because of the differences in starting material chemistry,trimethylolpropane-succinic anhydride reaction products are always moreviscous than glycerolpropoxylate-succinic anhydride reaction products.However, if same raw materials are used carboxyl polyol has lowestviscosity if there is one ester group per molecule of resulting carboxylpolyol. FIGS. 1 and 2 illustrate viscosity dependence on ester groupcontent per one carboxyl polyol molecule. Ester group content insubstance was measured as the difference between the acid number atbeginning of the reaction and the acid number of the carboxyl polyol.The Acid number at beginning of reaction was calculated from amounts oftriol and succinic anhydride used in reaction. The Acid number ofcarboxyl polyol was determined by titration with sodium hydroxidesolution using phenolphtalein indicator. Ester group content per onemolecule was calculated from ester group content in carboxyl polyol andmolecular weight (ester content as mgKOH/g times molecular weightdivided by constant 56100). Molecular weight used in calculations wasnumber average molecular weight as determined by GPC method. Carboxylpolyol in FIG. 1 containing 1.696 ester groups per molecule was obtainedusing method described in U.S. Pat. No. 5,863,980. Carboxyl polyol inFIG. 2 containing 5.162 ester groups per molecule also was obtainedusing method described in U.S. Pat. No. 5,863,980. These graphsdemonstrate advantages of present invention in producing the desired lowviscosity carboxyl polyols.

[0036] To further enhance the stability of the carboxyl-containingpolyols, the carboxyl group is suitably at least partially neutralizedwith an amine, such as triethylamine(“TEA”). Besides TEA, other usefulamines for neutralizing the carboxyl group on the carboxyl-containingpolyol include: trimethylamine, tripropylamine, tributylamine,triisopropylamine, dimethylamine, diethylamine, tripropylamine,dibutylamine, monoethanol amine, dimethylethanolamine, aminoalcohols,morpholine, n-methylmorpholine, n-ethylmorpholine, and combinationsthereof, alone or in combinations with other organic amines. Preferablythe neutralizing amine is a tertiary amine that will not react withisocyanate. Experimental polyol structures, including the TEA salt, are:

[0037] Neutralized carboxyl polyols with isocyanate proceeds fast evenat 60-70 C temperature range. All of these advantages in usingneutralized carboxyl polyols amount to substantial time and energysavings.

[0038] Preferably, the carboxyl-containing monomers are liquid at roomtemperature because liquids are easy to handle as compared to solids. Auseful range of viscosities for the carboxyl-containing monomers isgenerally less than 100,000 cps at 25° C. Preferably, the viscosity ofthe carboxyl-containing monomers is from about 3,000 to about 100,000cps, more preferably from about 3,000 to about 50,000 cps, and mostpreferably from about 3,000 to about 20,000 cps.

[0039] In order to increase the shelf life of prepolymer products madefrom the carboxyl-containing monomers, it is desirable that thecarboxyl-containing polyols made as described above contain minimalamounts of oligomers. As defined herein, oligomers are molecules whichresult from the reaction of the carboxyl function with another hydroxylfunction, which can lead to oligomerization of the monomer products.Oligomers are undesirable due to their propensity to cause increasedviscosity of the monomer product.

[0040] It has been found that the presence of oligomers above about 30mg KOH/g (as analyzed below) results in undesirable gelling of theprepolymer product. Preferably, the carboxyl-containing monomers haveless than 30 mg KOH/g oligomers, preferably between 2 and 30 mg KOH/goligomers, more preferably between 2 and 20 mg KOH/g oligomers, and mostpreferably between about 2 and 15 mg KOH/g oligomers. Oligomer contentin the carboxyl-containing monomer can be measured by calculating thedifference between theoretical acid number and acid number determined bychemical analysis as known in the art.

[0041] Briefly, acid number is determined using 1-2 grams of sample. 100ml of isopropyl alcohol and 50 ml water is added to the sample, andstirred until the sample is completely dissolved. Approximately 15 dropsof 1% phenolphthalein solution is added, and the sample solution istitrated with 0.5 N potassium hydroxide (or 0.5 N sodium hydroxide)until a light pink color appears. Oligomer content in thecarboxyl-containing monomer can be measured by calculating thedifference between theoretical acid number and acid number determined bychemical analysis (expressed as mg KOH/g sample). This difference in mgKOH/g is then correlated to oligomeric ester units per gram of monomer.

[0042] As indicated above, the carboxyl-containing polyols preparedabove may be used in the production of a “prepolymer”. In general, theprepolymer is made by combining the carboxyl-containing polyols preparedabove with a polyisocyanate compound. Organic polyisocyanates useful asreactants in the production of the prepolymer include any aromatic,cycloaliphatic and aliphatic diisocyanates and higher polyisocyanates.Diisocyanates are the preferred class of polyisocyanates. Suitablealiphatic diisocyanates include hexamethylene diisocyanate,4,4′-dicyclohexylmethane diisocyanate; isophorone diisocyanate;1,4′-tetramethylene diisocyanate; and 1,10-decamethylene disiocyanateand 1,12-dodecamethylene diisocyanate. Suitable aromatic diisocyanatesinclude tolulene-2,4- or 2,6-diisocyanate; 1,5-naphthalenediisocyanates; 4-methoxy-1,3-phenylene diisocyanate;4-chloro-1,3-phenylene diisocyanate; 2,4′-diisocyanatodiphenyl ether;5,6-dimethyl-1,3-phenylate diisocyanate; 2,4-diemthyl-1,3-phenylenediisocyanate; 4,4′diisocyanatodiphenylether; benzidene diisocyanate,4,4′-diisocyanataodibenzyl; methylene-bis(4-phenylisocyanate); and1,3-phenylene diisocyanate. Particularly useful polyisocyanates for usein preparing the polyurethane prepolymers include toluene diisocyanate,4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate,hexamethylene diisocyanate, isophorone diisocyanate,4,4′-dicyclohexylmethane diisocyanate, 1,12-dodecanediisocyanate,2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate,tetramethyl-xylylene diisocyanate and other polyisocyanates such aspolymethylene polyphenyl isocyanate and isocyanate prepolymers having atleast two isocyanate groups which are produced by reacting an isocyanatewith a polyhydroxyl compound such as polyoxyalkylene polyol or polyesterpolyol or mixtures thereof.

[0043] The reaction in which hydroxyl groups are reacted with isocyanategroups and polyurethane prepolymer is produced is usually performed at50-100° C. for 1-5 hours under an inert atmosphere such as nitrogen gasand at atmospheric pressure. Preferably the reaction is performed at60-90° C. for 2-3 hours.

[0044] The ratio of isocyanate to carboxyl-containing polyol is such asto have the desired amount of carboxyl groups per molecule ofpolyurethane prepolymer. Usually, the carboxyl-containing monomer isadded to result in an acid number for the prepolymer of 10-30 mg KOH/g.The preferred procedure for producing the prepolymer is to react theselected polyisocyanate with regular polyether or polyester polyol for1-2 hours at 80-90° C., and then add carboxyl-containing monomers andreact until the theoretical isocyanate group content has been reached.If desired, catalysts such as dibutyltin dilaurate, stannous octoate, oramine-type catalysts like triethylamine or triethylene diamine, may beused to assist prepolymer formation. The prepolymer composition may alsoinclude solvents such as acetone, methylethylketone,N-methylpyrrolidinone, and the like.

[0045] Because of the that way that carboxyl groups are added to thepolyol molecule, the resulting main polyurethane chain is linear withcarboxyl groups as side pendants. This structure is ideal for obtaininggood water-borne dispersions. The chemical structure of an exemplaryprepolymer made from 1 mole of 1000 molecular weight propylene oxidebased diol (Poly-G 20-112 from Arch Chemicals, Inc., Norwalk, Conn.),three moles of 4,4′ dicyclohexylmethane diisocyanate, and one mole oftrimethylolpropane with succinic anhydride added to a side chain is asfollows:

[0046] This prepolymer is easy to disperse in water by converting sidependant carboxyl groups into salt groups and then reacting free NCOgroups with diamine to obtain a high molecular weight urethanedispersion in water. Because, according to the present invention, thereis one carboxyl group added to each triol molecule, the resultingprepolymer has low viscosity, low oligomer content, and is very easy todisperse in water. The dispersion process proceeds easily andwater-borne dispersions may be prepared without the use of highshear/high speed mixers. It has been also discovered that becauseprepolymers made with carboxyl polyols have low viscosity anddicarboxylic acid monoesters which are on a side chain of polyurethanemolecule act as internal coalescing agents. Therefore, it is very easyto form solvent free polyurethane dispersions utilizing theseprepolymers.

[0047] The prepolymer, as described above, may be combined with an aminecompound to extend the prepolymer and further disperse the polymer inwater. Suitable amines for dispersing prepolymer in water and chainextending the prepolymer include triethylamine, tripropylamine, ethylenediamine, n-butylamine, diethylamine, trimethylamine, monoethanol amine,dimethylethanolamine, aminoalcohols, hydrazine, hexamethylene diamine,isophorone diamine, cyclohexane diamine, dimethylcyclohexylamine,tris(3-aminopropyl)amine, 2-methylpentamethylenediamine,1,12-dodecanediamine and combinations thereof.

[0048] The chain extension reaction occurs when free isocyanate groupsof water dispersed prepolymer react with amino groups and is describedin the art. The reaction between isocyanate groups and amine groups isvery fast and chain extension step can be carried out in water.

[0049] It may be desirable to add other conventional additives such asthickening agents, pH adjusters, monoisocyanates and the like to thecomposition of the invention. Furthermore, fillers, plasticizers,pigments, and the like may be utilized as desired. It may be alsodesirable to add other polyurethane prepolymers made from modified orunmodified polyether polyols or polyester polyols or the like.

EXAMPLES

[0050] The following examples are intended to illustrate, but in no waylimit the scope of the present invention. All parts and percentages areby weight and all temperatures are in degrees Celsius unless explicitlystated otherwise.

Example 1 Connecting Carboxyl Groups to Polyether Triol

[0051] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 1696 grams of polyol Poly-G 76-635 polyether triolwith OH number 635 made by Arch Chemicals, Norwalk, Conn.) and 0.45grams of 85% ortho phosphoric acid (Aldrich Chemical, St. Louis, Mo.).The mixture was stirred at room temperature for 30 minutes and then645.3 grams of succinic anhydride were added (Aldrich). With agitationthe working temperature was increased to 98° C. and the mixture heatedfor 2 hours. After 2 hours, a sample for acid number was taken andcompared to a theoretical value. With an acid number higher thantheoretical heating was continued and then sampled every half hour untilan acid number was 1 to 2 units from theoretical. When the acid numberwas in desired range the flask was cooled.

[0052] For comparison purposes, an experiment with the same polyol andsuccinic acid anhydride ratio except that this time no phosphoric acidwas added and reaction was performed according to the proceduredescribed in U.S. Pat. No. 5,863,980 (see Comparative Example 2 isbelow).

Comparative Example 2 Preparing Carboxyl Polyol with No Acid Present inAccordance with the Procedure of U.S. Pat. No. 5,863,980

[0053] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 398.5 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.) and152.7 grams of succinic anhydride (Aldrich). With nitrogen flow andagitation working the temperature was increased to 80° C. and themixture was heated for 1 hour. Then the temperature was slowly raised to135 C over time span of about 30 minutes, and reaction performed at thesame temperature for two hours. Product was heated at 135 C and vacuumstripped at −29 inches of mercury for 2 hours. Flask was cooled undervacuum.

[0054] The resulting polyols are compared in Table 1. TABLE 1 Comparisonof acid catalysis effect on carboxyl polyol synthesis Comp. Example 2Example 1 Formulation of: (Prior Art) (Present Invention) Triol UsedPolyether Polyol Polyether Polyol 76-635 from Arch 76-635 from ArchChemical Chemical H₃PO₄, ppm 0 227 Temp. (° C.) 135 98 Theoretical Acid155.2 155.2 Found Acid 120 153 Oligoester, mg KOH/g 35.2 2.2Oligoester/Acid 0.2933 0.014 OH # 289 321 PH 3.4 3.3 Viscosity at 25C16720 8800 MW by GPC 500 408 Calculated MW 361 361 MW Difference 139 47

[0055] The data in Table 1 show that the polyol obtained according tothe prior art was 1.9 times more viscous and contained 16 times moreoligoester units. Also there was significant difference between themolecular weight determined by GPC for this polyol and that calculatedfrom the formula. Polyol with carboxyl groups made according to thisinvention was less viscous, contained only few oligoester groups and themolecular weight determined by GPC was close to the theoreticalmolecular weight calculated.

[0056] Polyols obtained in experiments 1 and 2 above were reacted with2000 molecular weight polyether diol Poly-G 20-56 (made by ArchChemicals) and 4,4′-dicyclohexylmethane diisocyanate (Desmodur W made byBayer) to produce prepolymers (refer to the formulations described inComparative Example 3 and Example 4 in Table 2 below). Table 2 comparesproperties of the prepolymer obtained in the process of this invention(Example 4) with that obtained according to the process of U.S. Pat. No.5,863,980 (“Prior Art”) (Comparative Example 3). TABLE 2 PrepolymerComparison of Prior Art to Present Invention Experiment 3 Experiment 4(Prior Art) (Present Invention) Raw Materials Used Polyol of Comp. Exp.2, Polyol of Exp. 1, Polyether diol, Polyether diol, Poly-G 20-56,Poly-G 20-56, Desmodur W Desmodur W NCO/OH ratio 1.3 1.3 Acid # ofPrepolymer 30.8 31.3 NCO % Theoretical 2.06 2.00 NCO % After Reaction2.19 2.14 Viscosity at 25C 416,000 11,160 (measured after reaction) NCO% After 16 Hours gel 2.13 Viscosity at 25C gel 21,520 After 16 Hours

[0057] As can be seen in Table 2, prepolymer obtained from polyol madeaccording to U.S. Pat. No. 5,863,980 was 37 times more viscous thanprepolymer made with carboxyl containing polyol made through the currentinvention and eventually gelled after 15 hours. Table 3 contains data onthe results of connecting carboxyl groups to different triols by theaddition reaction of the present invention.

[0058] In Table 3, formulations and properties are provided forcompositions prepared in accordance with Example 1 above, and thesecompositions are identified in Table 3 as Examples 1, 5, 6, 7, and 12.The preparation for Example 8 is described below, and Examples 9, 10 and11 were prepared in accordance with the protocol given in Example 8.TABLE 3 Effect of connecting carboxyl groups to triols Example No. 1(above) 5 6 7 8 9 10 11 12 Triol Used Polyether Polyether PolyetherPolyether TMP TMP TMP TMP Polyether Polyol 76- Polyol 76- Polyol 76-Polyol 76- Polyol 635 635 635 635 35-610 from Arch Chemicals Phosphoric227 5 5 227 316 316 300 320 5 Acid ppm Temp. C 98 100 100 98 100 100 80103 80 Theoretical Acid # 155.2 155.2 155.2 155.2 239.5 239.5 239.5239.5 150.9 Found Acid # 153 150.7 146.7 149.3 224.5 219 227.5 213.4147.8 Oligoester, 2.2 4.5 8.5 5.9 15 20.5 12 26.1 3.1 mgKOH/gOligoester/ 0.014 0.030 0.058 0.0395 0.067 0.086 0.0527 0.1223 0.0209Acid OH # 321 322 311 316 449.7 451 455.3 439.7 300.7 Water % 0.2 0.30.05 .05 0.6 0.31 0.41 0.41 0.24 pH 3.3 3.1 3.1 3.3 3.2 3.1 3.1 3.1 3.2Viscosity at 25 C 8800 11500 12600 8840 97200 108400 77600 90800 4265 MWby GPC 408 392 405 408 302 297 315 287 374 Calculated MW 361 361 361 361234 234 234 234 371.9 MW Difference 47 31 44 47 68 63 81 53 2.1

Example 8 Addition Reaction Connecting Carboxyl Groups toTrimethylolpropane

[0059] To a flask equipped with thermometer, stirrer and refluxcondenser were added 1341.8 grams of trimetylolpropane (Aldrich).Without agitation the temperature was slowly increased to 95° C. to meltthe trimethylolpropane. To the melted trimethylolpropane melted wereadded 0.753 grams of 85% ortho phosphoric acid (Aldrich) and 1000.7grams of succinic anhydride (Aldrich). With agitation, the slurry washeated to and held at 100° C. until all solids were dissolved. As soonas there were no solids in the flask, it was sampled for acid number andcompared to the theoretical value. With acid number higher thantheoretical, heat was continued and sampled every 15 minutes till anacid number was 1 to 2 units from theoretical. When the acid number wasin desired range the flask was cooled.

Example 13 Preparation of Water-borne Polyurethane Dispersion

[0060] 38 grams of 4,4′-dicyclohexylmethane diisocyanate (“DESMODUR W”from by Bayer), 22.3 of polyether diol with molecular weight 425 (Poly-G20-265 from Arch Chemicals), 0.008 grams of dibutyltin dilaurate(catalyst Dabco T-12 from Air Products), and 18.7 grams ofmethylethylketone were mixed and heated to 85° C. and maintained at thattemperature for 1 hour. After 1 hour, 21 grams of carboxyl polyol wasadded. This carboxyl polyol was obtained by reacting 1 mol of Poly-G76-635 with 1 mol of succinic anhydride as described in Example 1, andhad an equivalent weight of 179.4 for each OH group, and an equivalentweight 381.6 for each carboxyl group. After adding the carboxyl polyol,heating was continued for 2 more hours at 85° C. The NCO content of theprepolymer was analyzed and found to be 3.08%. The warm prepolymer wasmixed at a high speed and then a mixture of 5.56 grams of triethylamineand 100 grams of water were added and mixed for 5 minutes to insurecomplete dispersion. No heating was applied at this stage. Temperaturein flask after adding triethylamine and water was 46-47° C. A solutionof 2.09 grams of ethylenediamine in 56.7 grams water was added to thedispersion and agitation was continued for 1 hour. The resultingdispersion was an opalescent liquid which after drying produced filmwith the following physical properties: Sward Hardness: 49; TensileStrength: 3720 psi; Elongation at break: 52%

Example 14 Preparation of Water-borne Polyurethane Dispersion

[0061] 62.07 grams of 4,4′-dicyclohexylmethane diisocyanate (“DESMODURW” from Bayer), 70 grams of polyether diol with molecular weight 1000(Poly-G 20-112 from Arch Chemicals), 0.062 grams of dibutyltin dilaurate(Dabco T-12 from Air Products), 39.25 grams of methylethylketone wasmixed and heated to 85° C. and maintained at that temperature for 1hour. After 1 hour, 28.87 grams of carboxyl polyol was added. Thiscarboxyl polyol was obtained by reacting 1 mol of trimethylolpropanewith 1 mol of succinic anhydride as described in Example 8 and hadequivalent weight 127.9 for each OH group and equivalent weight 268.4for each carboxyl group. After adding carboxyl polyol heating wascontinued for 2 more hours at 85° C. The NCO content of prepolymer wasanalyzed and found to be 2.34%. Warm prepolymer was mixed fast andmixture of 10.82 grams of triethylamine and 200 grams of water was addedand mixed for 5 minutes to insure complete dispersion. No heating toflask was applied at this stage. Temperature in flask after adding oftriethylamine and water was 49-50° C. Solution of 3.16 grams ofethylenediamine in 163.4 grams of water was added to dispersion andagitation was continued for 2 hours. The resulting dispersion wasopalescent liquid which after drying produced film with followingphysical properties: Sward Hardness: 29; Tensile Strength: 3960 psi;Elongation at break: 265%; 100% modulus: 2220 psi; Tear resistance: 265p/in.

Example 15 Preparing Carboxyl Polyol in Presence of Hydrochloric Acid

[0062] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 494.8 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.) and0.132 grams of 35% hydrochloric acid (Aldrich Chemical, St. Louis, Mo.).The mixture was stirred at room temperature for 10 minutes and then188.26 grams of succinic anhydride were added (Aldrich). With agitationthe working temperature was increased to 100° C. and the mixture washeated for 2 hours. After 2 hours, a sample for acid number was takenand compared to a theoretical value. With an acid number higher thantheoretical heating was continued and then sampled every half hour tillan acid number was 1 to 2 units from theoretical. When the acid numberwas in the desired range the flask was cooled.

Example 16 Preparing Carboxyl Polyol in Presence of Sulfuric Acid

[0063] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 494.8 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.) and0.060 grams of 100% sulfuric acid (Aldrich Chemical, St. Louis, Mo.).The mixture was stirred at room temperature for 10 minutes and then188.26 grams of succinic anhydride were added (Aldrich). With agitationthe working temperature was increased to 100° C. and the mixture washeated for 2 hours. After 2 hours, a sample for acid number was takenand compared to a theoretical value. With an acid number higher thantheoretical heating was continued and then sampled every half hour tillan acid number was 1 to 2 units from theoretical. When the acid numberwas in the desired range the the flask was cooled.

Example 17 Preparing Carboxyl Polyol in Presence of Nitric Acid

[0064] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 398.5 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.), 0.072grams of 70% nitric acid (Aldrich Chemical, St. Louis, Mo.) and 152.6grams of succinic anhydride were added (Aldrich). With agitation theworking temperature was increased to 100° C. and the mixture was heatedfor 2 hours. After 2.5 hours, a sample for acid number was taken andcompared to a theoretical value. With an acid number higher thantheoretical heating was continued and then sampled every half hour tillan acid number was 1 to 2 units from theoretical. When the acid numberwas in the desired range the flask was cooled.

[0065] Table 4 shows comparative results in the production of carboxylpolyols using phosphoric acid (Examples 1 and 5 above), hydrochloricacid (Example 15), sulfuric acid (Example 16), and nitric acid (Example17) as catalysts. TABLE 4 Properties of Carboxyl Polyols made inpresence of inorganic acid catalysts Exp. No. 1 5 15 16 17 Triol UsedPolyether Polyether Polyether Polyether Polyether Polyol 76-635 Polyol76-635 Polyol 76-635 Polyol 76-635 Polyol 76-635 Acid used PhosphoricPhosphoric Hydrochloric Sulfuric Nitric Acid ppm 227 5 193 88 130 Temp.° C. 98 98 100 100 100 Theoretical 155.2 155.2 155.2 155.2 155.2 Acid #Found Acid 153 150.7 154.4 153.8 154.4 # Oligomer 2.2 4.5 0.8 1.4 0.8mgOH/g Oligomer/ 0.0014 0.030 0.005 0.009 0.005 Acid OH# 321 322 332 334327 Water % 0.2 0.3 0.08 0.08 0.08 pH 3.3 3.1 3.3 3.2 3.4 Viscosity at8800 11500 7680 7280 9100 25 C MW by 408 392 455 460 453 GPC Calulated361 361 361 361 361 MW MW 47 31 94 99 92 Difference

Example 18 Preparation of Water-borne Polyurethane Dispersion

[0066] 52.85 grams of isophorone diisocyanate (“LUXATE IM” from LyondellChemical Co., Houston, Tex.), 69.4 grams of polyether diol withmolecular weight 1000 (Poly-G 20-112 made by Arch Chemicals, Norwalk,Conn.), 0.08 grams of dibutyltin dilaurate (Dabco T-12 from AirProducts, Allentown, Pa.), 39.25 grams of methylethylketone was mixedand heated to 85° C. and maintained at that temperature for 1 hour.After 1 hour 38.5 grams of polyol with carboxyl groups was added. Thiscarboxyl polyol was obtained by reacting 1 mol of polyether polyol76-635 with 1 mol of succinic anhydride in presence of hydrochloric acidas described in Example 15 and had equivalent weight 168.8 for each OHgroup and equivalent weight 358.7 for each carboxyl group. After addingpolyol with carboxyl groups heating was continued for 3 more hours at85° C. The NCO content of prepolymer was analyzed and found to be 2.16%.Warm prepolymer was mixed fast and mixture of 10.9 grams oftriethylamine and 300 grams of water was added and mixed for 5 minutesto insure complete dispersion. No heating to flask was applied at thisstage. Temperature in flask after adding of triethylamine and water was49-50° C. Solution of 8.29 grams of isophorone diamine in 200 grams ofwater was added to dispersion and agitation was continued for 2 hours.The resulting dispersion was opalescent liquid which after dryingproduced film with following physical properties: Sward Hardness: 24;Tensile Strength: 3780 psi; Elongation at break: 488%; 100% modulus: 910psi; Tear resistance: 244 p/in.

Example 19 Preparation of Water-borne Polyurethane Dispersion

[0067] 52.9 grams of isophorone diisocyanate (“LUXATE IM” from LyondellChemical Co., Houston, Tex.), 69.4 grams of polyether diol withmolecular weight 1000 (Poly-G 20-112 made by Arch Chemicals, Norwalk,Conn.), 0.1 grams of dibutyltin dilaurate (Dabco T-12 from Air Products,Allentown, Pa.), 39.25 grams of methylethylketone was mixed and heatedto 85° C. and maintained at that temperature for 1 hour. After 1 hour38.4 grams of polyol with carboxyl groups was added. This polyol withcarboxyl groups was obtained by reacting 1 mol of polyether polyol76-635 with 1 mol of succinic anhydride in presence of sulfuric acid asdescribed in Example 16 and had equivalent weight 167.8 for each OHgroup and equivalent weight 353.7 for each carboxyl group. After addingpolyol with carboxyl groups, heating was continued for 3 more hours at85° C. The NCO content of prepolymer was analyzed and found to be 2.26%.Warm prepolymer was mixed fast and mixture of 11 grams of triethylamineand 300 grams of water was added and mixed for 5 minutes to insurecomplete dispersion. No heating to flask was applied at this stage.Temperature in flask after adding of triethylamine and water was 49-50°C. Solution of 8.2 grams of isophorone diamine in 200 grams of water wasadded to dispersion and agitation was continued for 2 hours. Theresulting dispersion was opalescent liquid which after drying producedfilm with following physical properties: Sward Hardness: 24; TensileStrength: 3310 psi; Elongation at break: 470%; 100% modulus: 910 psi;Tear resistance: 270 p/in.

Example 20 Preparation of Water-borne Polyurethane Dispersion

[0068] 158.6 grams of isophorone diisocyanate (“LUXATE IM” from LyondellChemical Co., Houston, Tex.), 206.9 grams of polyether diol withmolecular weight 1000 (Poly-G 20-112 made by Arch Chemicals, Norwalk,Conn.), 0.6 grams of dibutyltin dilaurate (Dabco T-12 from Air Products,Allentown, Pa.), 117.8 grams of N-methylpyrrolidinone was mixed andheated to 85° C. and maintained at that temperature for 3 hours. After 3hours 116.8 grams of polyol with carboxyl groups was added. This polyolwith carboxyl groups was obtained by reacting 1 mol of polyether polyol76-635 with 1 mol of succinic anhydride in presence of nitric acid asdescribed in Example 17 and had equivalent weight 167.8 for each OHgroup and equivalent weight 363.3 for each carboxyl group. After addingpolyol with carboxyl groups heating was continued for 3 more hours at85° C. The NCO content of prepolymer was analyzed and found to be 2.55%.Viscosity at 25° C. was 42560 cP. This prepolymer was cooled to roomtemperature and used for preparation of water borne polyurethanedispersions as described in the following Examples.

Example 21 Preparation of Water Borne Polyurethane Dispersion

[0069] Prepolymer was made as described in Example 20. 300 grams ofwater at room temperature were placed in 1-liter flask equipped withmechanical stirrer, 0.1 grams of surfactant BYK 020 (BYK Chemie) and 5.4grams of triethylamine (Aldrich) were added to water. The contents ofthe flask was stirred and 91.1 grams of prepolymer was slowly added tothe flask. After all prepolymer has been dispersed in water, 2.87 gramsof cyclohexyl diamine was dissolved in 30 grams of water and drop wiseadded to dispersed prepolymer. The flask was stirred without heating for4 hours. The resulting dispersion was an opalescent liquid which afterdrying produced film with following physical properties: Sward Hardness24, Tensile Strength 2603 psi, Elongation at break 830%, 100% modulus381 psi, Tear resistance 88 p/in.

Example 22 Preparation of Water Borne Polyurethane Dispersion

[0070] Prepolymer was made as described in Example 20. 300 grams ofwater at room temperature was placed in 1-liter flask equipped withmechanical stirrer, 0.1 grams of surfactant BYK 020 (BYK Chemie) and 5.4grams of triethylamine (Aldrich) were added to the water. Contents ofthe flask was stirred, and 103.4 grams of prepolymer was slowly added tothe flask. After all the prepolymer has been dispersed in water 1.71grams of ethylenediamine was dissolved in 30 grams of water and dropwise added to disperse prepolymer. The flask was stirred without heating4 hours, The resulting dispersion was an opalescent liquid which afterdrying produced film with following physical properties: Sward Hardness22, Tensile Strength 1280 psi, Elongation at break 685%, 100% modulus240 psi, Tear resistance 77 p/in.

Example 23 Preparation of Water Borne Polyurethane Dispersion

[0071] Prepolymer was made as described in Example 20. 300 grams ofwater at room temperature were placed in 1-liter flask equipped withmechanical stirrer, 0.1 grams of surfactant BYK 020 (BYK Chemie) and 5.4grams of triethylamine (Aldrich) were added to the water. The contentsof the flask were stirred, and 99.7 grams of prepolymer was slowly addedto the flask. After all prepolymer has been dispersed in water, 4.7grams of isophorone diamine was dissolved in 30 grams of water and dropwise added to the dispersed prepolymer. The flask was stirred withoutheating 4 hours. The resulting dispersion was an opalescent liquid whichafter drying produced a film with following physical properties: SwardHardness 24, Tensile Strength 1745 psi, Elongation at break 526%, 100%modulus 291 psi, Tear resistance 87 p/in.

Example 24 Preparation of Water Borne Polyurethane Dispersion

[0072] Prepolymer was made as described in Example 20. 300 grams ofwater at room temperature were placed in a 1-liter flask equipped withmechanical stirrer, and 0.1 grams of surfactant BYK 020 (BYK Chemie) and5.4 grams of triethylamine (Aldrich) were added to the water. Thecontents of flask were stirred, and 114.5 grams of prepolymer was slowlyadded to the flask. After all prepolymer had been dispersed in water,2.88 grams of 35% hydrazine was dissolved in 30 grams of water and dropwise added to the dispersed prepolymer. The flask was stirred withoutheating 4 hours. The resulting dispersion was an opalescent liquid whichafter drying produced a film with following physical properties: SwardHardness 20, Tensile Strength 1020 psi, Elongation at break 860%, 100%modulus 218 psi, Tear resistance 73 p/in.

Example 25 Preparing Carboxyl Polyol in Presence of Formic Acid

[0073] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 398.5 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.) and0.126 grams of 96% formic acid (Aldrich Chemical, St. Louis, Mo.). Themixture was stirred at room temperature for 10 minutes and then 151.7grams of succinic anhydride were added (Aldrich). With agitation theworking temperature was increased to 100° C. and the mixture was heatedfor 4 hours. After 4 hours, a sample for acid number was taken andcompared to a theoretical value. With an acid number higher thantheoretical heating was continued and then sampled every half hour tillan acid number was 1 to 2 units from theoretical. When the acid numberwas in the desired range the flask was cooled.

Example 26 Preparing Carboxyl Polyol in Presence of Propionic Acid

[0074] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 398.5 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.), 0.126grams of 99% propionic acid (Aldrich Chemical, St. Louis, Mo.) and 151.7grams of succinic anhydride were added (Aldrich). With agitation theworking temperature was increased to 100° C. and the mixture was heatedfor 4 hours. After 4 hours, a sample for acid number was taken andcompared to a theoretical value. With an acid number higher thantheoretical heating was continued and then sampled every half hour tillan acid number was 1 to 2 units from theoretical. When the acid numberwas in the desired range the flask was cooled.

Example 27 Preparing Carboxyl Polyol in Presence of p-ToluenesulfonicAcidic

[0075] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 398.5 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.) and0.124 grams of 98% p-toluenesulfonic acid (Aldrich Chemical, St. Louis,Mo.). The mixture was stirred at room temperature for 10 minutes andthen 151.7 grams of succinic anhydride were added (Aldrich). Withagitation the working temperature was increased to 100° C. and themixture was heated for 4 hours. After 4 hours, a sample for acid numberwas taken and compared to a theoretical value. With an acid numberhigher than theoretical heating was continued and then sampled everyhalf hour till an acid number was 1 to 2 units from theoretical. Whenthe acid number was in the desired range the flask was cooled.

Example 28 Preparing Carboxyl Polyol in Presence of Oxalic Acid

[0076] To a flask equipped with a thermometer, stirrer and refluxcondenser were added 398.5 grams of polyol Poly-G 76-635 (polyethertriol with OH number 635 made by Arch Chemicals, Norwalk, Conn.) and0.127 grams of 98% oxalic acid (Aldrich Chemical, St. Louis, Mo.). Themixture was stirred at room temperature for 10 minutes and then 151.7grams of succinic anhydride were added (Aldrich). With agitation theworking temperature was increased to 100° C. and the mixture was heatedfor 4 hours. After 4 hours, a sample for acid number was taken andcompared to a theoretical value. With an acid number higher thantheoretical heating was continued and then sampled every half hour tillan acid number was 1 to 2 units from theoretical. When the acid numberwas in the desired range the flask was cooled.

[0077] As it is seen from the results given in Table 5, the illustrativeorganic acids can be used to produce carboxyl polyols with oligomercontent less than 2 mgKOH/g. These polyols with carboxyl groups areparticularly useful in waterborne polyurethane dispersions. TABLE 5Properties of Carboxyl Polyols made in presence of organic acidcatalysts Exp. No. 25 26 28 27 Triol Used Polyether Polyether PolyetherPolyether Polyol Polyol Polyol Polyol 76-635 76-635 76-635 76-635 Acidused Formic Propionic Oxalic p-toluene sulfonic Acid ppm 230 230 230 230Temp. C. 100 100 100 100 Theoretical 155.2 155.2 155.2 155.2 Acid #Found Acid # 154.5 154.5 153.2 153.6 Oligomer 0.7 0.8 1.0 1.6 mgKOH/gOligomer/ 0.005 0.005 0.006 0.01 Acid OH # 315 313 312.5 312 Water %0.19 0.15 0.19 0.26 PH 3.3 3.3 3.3 3.3 Viscosity at 9600 9500 1002010040 25C Mol weight 346 361 390 389 by GPC Calculated 361 361 361 361mol weight Mol weight 15 0 29 28 difference

Example 29 Preparing of 100% Neutralized Carboxyl Polyol

[0078] To a flask equipped with a thermometer, stirrer, reflux condenserand nitrogen inlet were added 506.9 grams of polyol Poly-G 76-635(polyether triol with OH number 635 made by Arch Chemicals, Norwalk,Conn.) and 0.14 grams of 95% phosphoric acid (Aldrich Chemical, St.Louis, Mo.). The mixture was stirred at room temperature for 10 minutesand then 192.9 grams of succinic anhydride were added (Aldrich). Withagitation the working temperature was increased to 100° C. and themixture was heated for 4 hours. After 4 hours, a sample for acid numberwas taken. Heating was continued and then sampled every half hour tillan acid number was 150 to 152 units. When the acid number was in thedesired range the flask was cooled to 80 C. With good mixing and usingan addition funnel 202 grams of triethylamine was added in such rate asnot to exceed 85 C temperature in flask. After all triethylamine wasadded the mixing and cooling was continued till temperature in flask was50 C or less.

Example 30 Preparing Polyurethane Dispersion Using 100% NeutralizedCarboxyl Polyol

[0079] 52.5 grams of isophorone diisocyanate (“LUXATE IM” from LyondellChemical Co., Houston, Tex.), 115.6 grams of polyether diol withmolecular weight 2000 (Poly-G 20-56 made by Arch Chemicals, Norwalk,Conn.), 0.01 grams of dibutyltin dilaurate (Dabco T-12 from AirProducts, Allentown, Pa.), 50 grams of methyl ethyl ketone was mixed andheated to 80° C. and maintained at that temperature for 3 hours. After 3hours 31.8 grams of 100% neutralized carboxyl polyol obtained as inexample 51 was added. This polyol with carboxyl had equivalent weight219 for each OH group and equivalent weight 474 for each carboxyl group.After adding polyol with carboxyl groups heating was continued for 1.5more hours at 80° C. The NCO content of prepolymer was analyzed andfound to be 3.67%. This prepolymer was cooled to 65 C temperature and250 grams of room temperature water was added in 2-3 minutes with goodmixing. Prepolymer dispersion in water was later reacted with solutionof 5.99 ethylene diamine in 131.5 grams of water. This ethylenediamine-water solution was slowly added thru addition funnel during 8-10minutes with good agitation. Mixing was continued till no isocyanategroups could be found by IR method. The resulting dispersion was anopalescent liquid which after drying produced a film with followingphysical properties: Sward Hardness 20, Tensile Strength 4180 psi,Elongation at break 790%, 100% modulus 660 psi, Tear resistance 240p/in.

Example 31 Preparing of 50% Neutralized Carboxyl Polyol

[0080] To a flask equipped with a thermometer, stirrer, reflux condenserand nitrogen inlet were added 506.9 grams of polyol Poly-G 76-635(polyether triol with OH number 635 made by Arch Chemicals, Norwalk,Conn.) and 0.14 grams of 95% phosphoric acid (Aldrich Chemical, St.Louis, Mo.). The mixture was stirred at room temperature for 10 minutesand then 192.9 grams of succinic anhydride were added (Aldrich). Withagitation the working temperature was increased to 100° C. and themixture was heated for 4 hours. After 4 hours, a sample for acid numberwas taken. Heating was continued and then sampled every half hour tillan acid number was 150 to 152 units. When the acid number was in thedesired range the flask was cooled to 80 C. With good mixing and usingan addition funnel 101 grams of triethylamine was added in such rate asnot to exceed 85 C temperature in flask. After all triethylamine wasadded the mixing and cooling was continued till temperature in flask was50 C or less.

Example 32 Preparing Polyurethane Dispersion Using 50% NeutralizedCarboxyl Polyol

[0081] 200 grams of 4,4′-dicyclohexylmethane diisocyanate (“DESMODUR W”from Bayer), 257 grams of polyether diol with molecular weight 2000(Poly-G 20-56 made by Arch Chemicals, Norwalk, Conn.), 0.2 grams ofdibutyltin dilaurate (Dabco T-12 from Air Products, Allentown, Pa.), 137grams of N-methylpyrrolidinone was mixed and heated to 85° C. andmaintained at that temperature for 2 hours. After 2 hours 105.9 grams of50% neutralized carboxyl polyol obtained as in example 53 was added.This carboxyl polyol had equivalent weight 209.5 for each OH group andequivalent weight 424 for each carboxyl group. Reaction mixture wascooled to 60 C. After adding polyol with carboxyl groups heating wascontinued for 5 more hours at 60° C. Prepolymer was cooled to roomtemperature and kept under nitrogen blanket over night. The NCO contentof prepolymer was analyzed and found to be 4.86%. Viscosity at 25 Ctemperature was 2520 cp. 210 grams of this prepolymer were added to 240grams of room temperature with good mixing. Prepolymer dispersion inwater was later reacted with solution of 6.93 g ethylene diamine in 53grams of water. This ethylene diamine-water solution was slowly addedthru addition funnel during 8-10 minutes with good agitation. Mixing wascontinued till no isocyanate groups could be found by IR method. Theresulting dispersion was an opalescent liquid which after dryingproduced a film with following physical properties: Sward Hardness 32,Tensile Strength 5500 psi, Elongation at break 470%, 100% modulus 2100psi, Tear resistance 435 p/in.

Example 33 Preparing Polyurethane Dispersion Using 50% NeutralizedCarboxyl Polyol

[0082] 391.6 grams isophorone diisocyanate (“LUXATE IM” from LyondellChemical Co. Houston, Tex.), 418.2 grams of polyether diol withmolecular weight 100 (Poly-G 20-112 made by Arch Chemicals, Norwalk,Conn.), 0.029 grams of dibutyltin dilaurate (Dabco T-12 from AirProducts, Allentown, Pa.), 274 grams of N-methylpyrrolidinone was mixedand heated to 85° C. and maintained at that temperature for 2 hours.After 2 hours 316 grams of 50% neutralized carboxyl polyol obtained asin example 53 was added. This carboxyl polyol had equivalent weight209.5 for each OH group and equivalent weight 424 for each carboxylgroup. Reaction mixture was cooled to 60 C. After adding polyol withcarboxyl groups heating was continued for 2 more hours at 60° C.Prepolymer was cooled to room temperature and kept under nitrogenblanket over night. The NCO content of prepolymer was analyzed and foundto be 3.65%. Viscosity at 25 C temperature was 5680 cp. 315 grams ofthis prepolymer were added to 360 grams of room temperature with goodmixing. Prepolymer dispersion in water was later reacted with solutionof 16.64 g isophorone diamine in 80 grams of water. This isophoronediamine-water solution was slowly added thru addition funnel during 8-10minutes with good agitation. Mixing was continued till no isocyanategroups could be found by IR method. The resulting dispersion was anopalescent liquid which after drying produced a film with followingphysical properties: Sward Hardness 26, Tensile Strength 5550 psi,Elongation at break 315%, 100% modulus 2150 psi, Tear resistance 270p/in.

Example 34 Preparing Solvent Free Polyurethane Dispersion Using 50%Neutralized Carboxyl Polyol

[0083] 124.7 grams isophorone diisocyanate (“LUXATE IM” from LyondellChemical Co., Houston, Tex.), 164.45 grams of polyether diol withmolecular weight 100 (Poly-G 20-112 made by Arch Chemicals, Norwalk,Conn.), 0.014 grams of dibutyltin dilaurate (Dabco T-12 from AirProducts, Allentown, Pa.) was mixed and heated to 85° C. and maintainedat that temperature is, for 2 hours. After 2 hours 85.5 grams of 50%neutralized carboxyl polyol obtained as in example 53 was added. Thiscarboxyl polyol had equivalent weight 209.5 for each OH group andequivalent weight 424 for each carboxyl group. Reaction mixture wascooled to 60 C. After adding polyol with carboxyl groups heating wascontinued for 2 more hours at 60° C. After that reaction timetemperature in flask was gradually raised to 70 C during 10-15 minutesperiod. Prepolymer was analyzed and found to have NCO %=4.6. Viscosityof prepolymer at 70 C was 6800 cp. 261 grams of this prepolymer at 70 Ctemperature were added to 401 grams of temperature at 40 C temperaturewith good mixing. Prepolymer dispersion in water was later reacted withsolution of 11.39 g isophorone diamine in 90 grams of water. Thisisophorone diamine-water solution was slowly added thru addition funnelduring 8-10 minutes with good agitation. Mixing was continued till noisocyanate groups could be found by IR method. The resulting dispersionwas an opalescent liquid which after drying produced a film withfollowing physical properties: Sward Hardness 16, Tensile Strength 4670psi, Elongation at break 455%, 100% modulus 990 psi, Tear resistance 185p/in.

[0084] Although the invention has been shown and described with respectto illustrative embodiments thereof, it should be appreciated that theforegoing and various other changes, omissions and additions in the formand detail thereof may be made without departing from the lo spirit andscope of the invention as delineated in the claims. All patents andpatent applications mentioned are herein incorporated by reference intheir entirety.

What is claimed is:
 1. A low viscosity carboxyl-containing polyol composition having a viscosity in the range of about 3,000-100,000 centipoise, and having an oligomer content of less than 30 mg KOH/g.
 2. A low viscosity carboxyl-containing polyol amine salt having a viscosity in the range of about 3,000-100,000 centipoise, and having an oligomer content of less than 30 mg KOH/g, said carboxyl being neutralized with an organic amine to provide said carboxyl-containing polyol amine salt.
 3. A method for producing the carboxyl-containing polyol of claim 1 comprising reacting a low molecular weight triol with an acid anhydride in the presence of 5-500 ppm of an organic or inorganic acid catalyst.
 4. The method of claim 3 wherein said organic or inorganic acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, formic acid, proprionic acid, p-toluenesulfonic acid, oxalic acid, and combinations thereof.
 5. The carboxy-containing monomer of claim 3, wherein said triol compound is selected from the group consisting of glycerol, trimethylolpropane, trimethylolethane, polyether polyols, and combinations thereof.
 6. The carboxy-containing monomer of claim 1, wherein said acid anhydride is selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, and mixtures thereof.
 7. The carboxy-containing monomer of claim 1, wherein said carboxyl-containing monomer is made in the presence of 50-250 ppm of said organic or inorganic acid.
 8. The carboxy-containing monomer of claim 7, wherein said carboxyl-containing monomer is made in the presence of 100-200 ppm of said organic or inorganic acid.
 9. The carboxy-containing monomer of claim 1, wherein said viscosity of said carboxyl-containing monomer ranges from 3,000 to 50,000 cps.
 10. The carboxy-containing monomer of claim 9, wherein said viscosity of said carboxyl-containing monomer ranges from 3,000 to 20,000 cps.
 11. The carboxy-containing monomer of claim 1, wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 30 mg KOH/g.
 12. The carboxy-containing monomer of claim 11, wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 20 mg KOH/g.
 13. A method of preparing a carboxyl-containing monomer for use in preparation of a polyurethane polymer, comprising the step of combining a low molecular weight polyol compound and an acid anhydride, in the presence of 25-500 ppm of an organic or inorganic acid, to produce said carboxyl-containing monomer, said carboxyl-containing monomer having a viscosity in the range of about 3,000 to about 100,000 cps and having a free oligomer content of sol less than about 30 mg KOH/g.
 14. The method of claim 13, wherein said low molecular weight polyol compound comprises from two to four hydroxyl groups.
 15. The method of claim 14, wherein said low molecular weight polyol compound is a triol compound possessing three hydroxyl groups.
 16. The method of claim 15, wherein said triol compound is selected from the group consisting of glycerol, trimethylolpropane, trimethylolethane, polyether polyols, and combinations thereof.
 17. The method of claim 16, wherein said low molecular weight polyol compound is a polyether triol.
 18. The method of claim 13, wherein said acid anhydride is selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, and mixtures thereof.
 19. The method of claim 13, wherein said carboxyl-containing monomer is made in the presence of about 50-250 ppm of said organic or inorganic acid.
 20. The method of claim 19, wherein said carboxyl-containing monomer is made in the presence of an organic or inorganic acid selected from the group consisting of. hydrochloric acid, sulfuric acid, nitric acid, formic acid, propionic acid, p-toluenesulfonic acid, oxalic acid, and combinations thereof.
 21. The method of claim 13, wherein said viscosity of said carboxyl-containing monomer ranges from about 3,000 to 50,000 cps.
 22. The method of claim 21, wherein said viscosity of said carboxyl-containing monomer ranges from about 3,000 to 20,000 cps.
 23. The method of claim 13, wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 30 mg KOH/g.
 24. The method of claim 23, wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 20 mg KOH/g.
 25. A prepolymer for use in preparing a polyurethane polymer, said prepolymer being the reaction product of (1) the carboxyl-containing monomer of claim 1, and (2) a polyisocyanate compound, said prepolymer having a viscosity in the range of about 3,000 to about 100,000 cps.
 26. The prepolymer of claim 25, wherein said polyisocyanate is selected from the group consisting of diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4′-tetramethylene diisocyanate, 1,10-decamethylene disiocyanate, 1,12-dodecamethylene diisocyanate, tolulene-2,4- or 2,6-diisocyanate, 1,5-naphthalene diisocyanates, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4′-diisocyanatodiphenyl ether, 5,6-dimethyl-1,3-phenylate diisocyanate, 2,4-diemthyl-1,3-phenylene diisocyanate, 4,4′-diisocyanatodiphenylether, benzidene diisocyanate, 4,4′-diisocyanataodibenzyl, methylene-bis(4-phenylisocyanate), 1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,12-dodecanediisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethyl-xylylene diisocyanate, polymethylene polyphenyl isocyanate, and combinations thereof.
 27. A prepolymer for use in preparing a polurethane polymer, said prepolymer being the reaction product of (1) carboxyl-containing polyol amine salt of claim 2, and (2) a polyisocyanate compound, said prepolymer having a viscosity in the range of about 3,000 to about 100,000 cps.
 28. The prepolymer of claim 27, wherein said polyisocyanate compound is selected from the group consisting of diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4′-tetramethylene diisocyanate, 1,10-decamethylene disiocyanate, 1,12-dodecamethylene diisocyanate, tolulene-2,4- or 2,6-diisocyanate, 1,5-naphthalene diisocyanates, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4′-diisocyanatodiphenyl ether, 5,6-dimethyl-1,3-phenylate diisocyanate, 2,4-diemthyl-1,3-phenylene diisocyanate, 4,4′-diisocyanatodiphenylether, benzidene diisocyanate, 4,4′-diisocyanataodibenzyl, methylene-bis(4-phenylisocyanate), 1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,12-dodecanediisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethyl-xylylene diisocyanate, polymethylene polyphenyl isocyanate, and combinations thereof.
 29. A water-borne polyurethane polymer, said water-borne polyurethane polymer being the reaction product of (1) the prepolymer of claim 25, and (2) an amine compound.
 30. The water-borne polyurethane polymer of claim 29, wherein said amine compound is selected from the group consisting of: triethylamine, tripropylamine, ethylene diamine, n-butylamine, diethylamine, trimethylamine, monoethanol amine, dimethylethanolamine, aminoalcohols, hydrazine, hexamethylene diamine, isophorone diamine, cyclohexane diamine, dimethylcyclohexylamine, tris(3-aminopropyl)amine, 2-methylpentamethylenediamine, 1,12-dodecanediamine, and combinations thereof.
 31. A prepolymer combination comprising the prepolymer of claim 25 and the prepolymer of claim
 27. 